TWI324103B - Method of manufacturing a replica as well as a replica obtained by carrying out an uv light-initiated cationic polymerization - Google Patents

Description

1324103 (1) 玖, description of the invention (the description of the invention should be described: the technical field, prior art, content of the invention, and the simple description of the drawings) [Technical Field] The present invention relates to a method for preparing a stamp, the method An impression comprising a polymerizable resin composition between a mold having a preformed surface and a mold having a preformed surface, a curing treatment, and removal from the mold, wherein the stamp is prepared The stamp contains a solid body in which the surface shape of the front mold and the surface shape of the subsequent mold are reproduced. The invention further relates to an impression obtained by performing uv light initiation cation polymerization. [Prior Art] Such a method is known from the specification of U.S. Patent No. 4,890,905, which is incorporated herein by reference. The stamping process uses a mold or stencil having a well defined surface profile that is the negative of the intended optical profile of the stamp. If the surface profile of the mold or stencil is to be accurately measured, it is necessary to take into account the amount of shrinkage of the synthetic resin of the stamp. Some liquid, curable synthetic resin composition is provided in the mold. The mold having a front portion and a rear portion is closed so that the synthetic resin is interspersed between the preformed surfaces of the two portions of the mold. This synthetic resin mixture is cured and the stamp is formed. The stamp is then removed from the mold. The surface of the synthetic resin stamp is a negative image of the surface of the two portions of the corresponding mold. An advantage of the stamping process is that optical components, such as lenses having complex refractive surfaces, such as a non-spherical surface, can be prepared in a relatively simple manner without subjecting a substrate, such as glass, to complex grinding processes. To get the desired surface shape. Such a disadvantage of using aggregation to replicate 1324103

The flow of matter is caused by (2) shrinkage. In particular, if the bondable resin combination gelation or a substantial increase in viscosity is impeded, further polymerization can result in stress generation or even early delamination. If the product is subsequently removed from the mold, particularly as in the case of an impression process, the stress will only partially relax, especially if the product formed is formed by a high density history polymer network. However, such a bonded polymer network is ultimately desirable for the cohesive force of the resulting product. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polymerizable resin composition in which, if it is cured against a mold, it exhibits as little relaxation as possible after being removed from the mold, and thus exhibits It may be accurate to the shape of the town two. Another method that is not praised is the use of a polymerizable resin composition that also features a high reaction rate that can be controlled by UV light. A further object of the present invention is to provide a method for preparing a stamp, "the middle spoon gathers" the tree is substantially insensitive to oxygen during curing, so that part is not completely covered, ^ a β _楗The enclosed resin is still curable in the ambient air, thereby avoiding the need to enclose the mold with an inert gas. A method of preparing an impression that the final product conforms to the current quality requirements. Still another object of the present invention is to provide a method for applying a polymerizable resin in combination with luminosity and hardness to a useful product of the present invention, further to the method of the present invention, 1324103 0), wherein a polymerizable resin composition is applied , the viscosity is very low, so that the amount of input can be guessed in the stamping process without any problem. The method of the method mentioned in the preceding paragraph is unconditional & Photoinitiative cationic polymerization, the resin composition used is a compound containing at least two cationically polymerizable cyclohexyl rings, which only occurs when at least 3% conversion has occurred. The indication of the action of the king's rubber can be achieved in the mold under suitable curing conditions. By utilizing such a bondable resin composition, the final product will be substantially free of shrinkage stress due to delayed gelation and relatively small amount of shrinkage. According to the petitioner, this relatively low level of shrinkage is helpful for the fact that the current dng-opemng process of the servant's U-treatment does not lead to a significant number of chemical bonds. The change, on the contrary, the number of chemical bonds in the starting product and the number of chemical bonds in the bonding product correspond to each other, so that only a small degree of shrinkage occurs. Conversely, in the known (meth)propionic acid brewing compound, it is known from the aforementioned specification of U.S. Patent No. 4,890,905, which causes an increase in the number of chemical bonds, which explains the reason for a large degree of shrinkage. . Further, in the compound according to the present invention, gelation and vitrification do not occur until a high conversion percentage is reached. Therefore, the generation of stress will be opened at a very late stage. According to the Applicant, this surprising effect is due to the unexpectedly large amount of chain transfer, so that at the beginning of the bonding reaction, relatively small molecules are formed which do not form a gel until they reach a high level. Conversion percentage. If the method according to the invention is applied to copy a hemispherical lens such as a CD player, call 4103

The use of the bondable composition according to the present invention results in the shape of the mold being substantially identical to the final formed product, so that the shrinkage correction required is much smaller. Moreover, less relaxation is required after the product is removed from the mold. It is expected that the amount expanded in the replicated lens shape will be much smaller in the aforementioned manufacturing process. The method according to the invention is particularly suitable for the replication of structures which require precise (sub-micron) replicated surface irregularities. A compound which can be suitably used in the preparation of a stamp according to the method of the present invention comprises a bondable resin composition of the formula: (X) a Z - (R2) m - 〇 - (^-1 )c

(R-Oc-〇-(R2)n —Ζ where: Υ=-0_, -S〇2- ' -CH2-, -C(CF3)2-, -C(CH3)2- '-C(= 0)- ' -0-C(=0)-, -〇-C(=0)-0-, halogen or ch3, KH2-, -C(CH3)2-, R2=-OCH2CH2-, -OCCH3HCH2- , -OCH2CCH3H·, _OCH2CHOHCH2-, r3 Z =-CHrC-[CH2]po R3=H, CnH2n+1, 1324103

(6) A proper impression is a structure that requires accurate (sub-micron) reproduction of any surface of the finished product. A further example of a suitable stamp is an optical member', particularly a (non)spherical lens, a lens array, a prism, a shutter or other optically applied surface uneven structure or a combination thereof. These and other aspects of the invention will be apparent from the description and appended claims. [Embodiment] Comparative Example 1 An aspherical lens is prepared by a generally familiar optical stamping method, which provides a reaction mixture containing a monomer, a photoinitiator, and, if desired, a sensitizer. The aspherical mold is pressed and pressed so that the liquid spreads between the preformed surface of a front mold and the preformed surface of a rear mold without containing bubbles. Then, the reaction mixture is exposed to υν light originating from a high-pressure mercury lamp and penetrating at least one of the front mold and the rear mold. The high-pressure mercury lamp is equipped with a filter such that the spectral range is only in the range of 320 to 390 nm. The light can be emitted. If necessary, the exposure process can be performed in the case where UV light penetrates both the front mold and the rear mold, provided that both molds have a form that can transmit light. After the exposure process, the lenses are removed from the molds and optically and mechanically tested. The above optical impression method utilizes a 2,2-dimethoxygen in a 2,2-bis(4-(2-isobutyl-oxoethoxy)-phenyl)propane. The reaction mixture of a solution of bis-12-diphenylethane-1-one (2,2-dimethyloxy-l,2-diphenylethane-l-〇n) is carried out. This mixture is at 40 mW/cm 2 (mw/cm 2 ) at room temperature -11 - 1324103

The intensity was exposed for 7 seconds and then removed' and then exposed to 1 〇mW/cm 2 for 1 hour at room temperature and allowed to stand in the dark for 16 hours at 140 °C. The lenses obtained in this way have optical and mechanical properties. The mixture exhibited a shrinkage of about 7% during the polymerization process. Using such a reaction mixture, the aspherical mold must be calibrated in a repetitive process to obtain a lens of the desired shape. The generally familiar optical impression method described in the above comparative examples is used in accordance with an embodiment of the present invention 'except that the reaction mixture used is one in 2,2-bis(4-(glycidyloxy)phenyl)propane It has 4.75% diphenyliodoniumhexafluoroarsenate and 0.25% anthracene solution. The mixture was then exposed to an intensity of 1 〇〇mW/cm 2 for 7 seconds at room temperature and then removed, then re-exposed at 10 mW/cm 2 for 1 hour at room temperature and allowed to stand at 110 ° C. 8 hours in the dark. The lenses obtained in this way have optical and mechanical properties. The mixture exhibited a shrinkage of about 2.3% during the polymerization process. The use of such a reaction mixture containing a compound comprising at least two cationically polymerizable cycloethyl ether groups is not required, or is almost unnecessary, and the reaction mixture as used in the comparative example is generally corrected for the aspherical mold. In order to obtain a lens of the desired shape. This advantageous result is helpful for the fact that almost no stress relaxation occurs after removal from the mold. This very small degree of stress relaxation contributed to the combination of reducing the amount of shrinkage and delaying the action of the gel according to the applicant, as compared with the reaction mixture used in the comparative example. -12 - 1324103 (8) The apparatus for preparing the lenses preferably comprises at least one of the molds being moved in the axial direction during the curing process, as disclosed in U.S. Patent No. 4,477,328. The addition of the monomer may be performed during the curing, as disclosed in U.S. Patent No. 4,812,346.

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Claims (1)

Announcement No. 092100318, the method of applying for the application of the patent range, the method comprising: - providing a pre-formed dimeric mantle and a pre-formed surface after the mold is provided - ° U9 The composition is subjected to a curing process and removed from the molds in such a manner that g @,, p杈, the stamp contains a solid body, wherein the surface shape of the mold and the surface shape of the back mold are heavy Now, ',' is characterized in that the curing treatment system - the resin composition used for the initiation of cationic polymerization of UV light is a compound which is substantially insensitive to oxygen (no inert gas is required), and the compound is derived from the following formula Representation: Z-(R2)m—〇—(R,) <Ri)c-〇-(R2)irz where: Y=-0-, -S02-, -CH2-, -C(CF3)2-, -C(CH3)2-, -C(=0)-, -0-C(=0)-, -0 -C(=0)-0-, X=halogen or CH3, R!=-CH2- '-C(CH3)2- > R2=-OCH2CH2-'-OCCH3HCH2- '-OCH2CCH3H- '-OCH2CHOHCH2- &gt ; Rj Z = -CH2-C-[CH2]p — 0 1^24103 _ •y _ ΐ »»Patent range i page i 0 R3 = H, CnH2n+ 1 ' n=Integer greater than or equal to 1, p= 1 - 4, m, a, b, c are each an integer ranging from 0-4, which only shows signs of gelation occurring at least 30% of the conversion has occurred, and the transformation can occur in the mold Reached under curing conditions. 2. The method of claim 1, wherein the resin composition further comprises a reaction diluent. 3. The method of claim 1 or 2, wherein the compound is selected from the group consisting of 1,2,7,8-diepoxyoctane and 3,4-epoxycyclohexylmethyl-3'. 4'-epoxyhydroxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyldecyl) adipate, bis-(3,4-epoxy-6-fluorenylcyclohexylfluorenyl) Adipate and C12-C14-alkyl glyceryl ether and their corresponding oxetane compounds, in particular propylene oxide compounds are 1,4-bis[(3-ethyl-3-oxocycle) Butyryl decyloxy) fluorenyl] benzene. 4. The method of claim 1 or 2, characterized in that the diluent used for the reaction is composed of a compound selected from the group consisting of a butyl glycerol bond, a heptyl glyceryl ether, and an octylglycerol. Ether, propyl glycerol scale, p-tertiary-butyl phenyl glyceryl ether, phenyl glyceryl ether, cresyl glyceryl ether, diglyceryl ether of 1,4-butanediol, diglyceryl ether of neopentyl glycol , propylene glycol diglyceryl ether, ethylene dioxane hexanol, recorcinol diglycerin test, polypropylene glycol diglyceryl ether and linoleic acid dimer diglyceride and its corresponding oxetane compound . 5. A stamp having a modified stencil of the patent application scope of claim 1, wherein the stamp has a surface on at least one side of the stamp. For rugged structures, the rugged surface must conform to the high standard (sub-micron) requirements for shape accuracy. 6. The stamp of claim 5, wherein the stamp obtained is an optical member. 7. The stamp of claim 6, wherein the resulting optical component is a (non)spherical lens, a lens array, a cymbal, a shutter or other optical application having an uneven surface. Structure, or a combination thereof. 8. The stamp of claim 5, wherein the compound is selected from the group consisting of 1,2,7,8-bisepoxyoctane, 3,4-epoxycyclohexyldecyl-3Ά-epoxy Hydroxycyclohexane carboxylate, bis-(3,4-epoxycyclohexylmethyl) adipate, bis-(3,4-epoxy-6-fluorenylcyclohexylmethyl) adipate And a C12-C14-alkyl glyceryl ether and its corresponding oxetane compound, in particular the propylene oxide compound is 1,4-bis[(3-ethyl-3-oxetanyloxy)oxyl Base) methyl] benzene. 9. The stamp of claim 5, characterized in that the diluent used for the reaction is composed of a compound selected from the group consisting of butyl glycerin scale, heptyl glycerol mystery, and octylglycerin. , allyl glyceryl ether, p-tertiary-butyl phenyl glyceryl ether, phenyl glyceryl ether, methionol ether, diglyceryl ether of 1,4-butanediol, diglyceryl ether of neopentyl glycol, A diglycerin mystery of polypropylene glycol, a vinyl dioxane, a diglycerin scale of recorcinol, a diglyceryl ether of polypropylene glycol, and a diglyceryl ether of a linoleic acid dimer and a corresponding oxetane compound thereof.